JPH02138431A - Single crystal ni-base super heat resistant alloy - Google Patents
Single crystal ni-base super heat resistant alloyInfo
- Publication number
- JPH02138431A JPH02138431A JP1030172A JP3017289A JPH02138431A JP H02138431 A JPH02138431 A JP H02138431A JP 1030172 A JP1030172 A JP 1030172A JP 3017289 A JP3017289 A JP 3017289A JP H02138431 A JPH02138431 A JP H02138431A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- phase
- creep rupture
- rupture strength
- oxidation resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 74
- 239000000956 alloy Substances 0.000 title claims abstract description 74
- 239000013078 crystal Substances 0.000 title claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 26
- 238000007254 oxidation reaction Methods 0.000 abstract description 26
- 229910052721 tungsten Inorganic materials 0.000 abstract description 14
- 229910052715 tantalum Inorganic materials 0.000 abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 4
- 229910052735 hafnium Inorganic materials 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 239000006104 solid solution Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000005496 eutectics Effects 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- 238000005275 alloying Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000601 superalloy Inorganic materials 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は主としてガスタービンエンジンのブレードに用
いられる、クリープ破断強度および耐酸化性のすぐれた
単結晶Ｎｉ基超超耐熱合金関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a single-crystal Ni-based ultra-super heat-resistant alloy with excellent creep rupture strength and oxidation resistance, which is mainly used for gas turbine engine blades.
一般に金属の高温での＠壊は結晶粒界で起こるため、タ
ービンブレードを結晶粒界の存在しない単結晶組織とし
、かつ適切な熱処理を行なうことによりその高温でのク
リープ破断強度は大幅に向上する。この概念に基づ＠
Ｕｎｉｔｅｄ ＴｅｃｈｎｏｌｏｇｉｅｓＣｏｒｐｏｒ
ａｔｉｏｎより、Ａ１１ｏｙ４４４．（米国特許第４．
．１１６，７２３号に記載）、Ａ１．１ｏｙ４５４（米
国特許第４，２０９，３４８号に記載）、Ａ１１ｏｙ２
０３Ｅ（米国特許第４，２２２，７９４号に記載）、Ａ
ｉｒ Ｒｅ５ｅａｒｃｈ Ｃｏｒｐｏｒａｔ、ｉｏｎよ
りＮＡＳＡＩＲｌｏｏ。Generally, fracture of metals at high temperatures occurs at grain boundaries, so by creating a turbine blade with a single-crystal structure without grain boundaries and performing appropriate heat treatment, its creep rupture strength at high temperatures can be greatly improved. . Based on this concept @
United Technologies Corporation
ation, A11oy444. (U.S. Patent No. 4.
．． 116,723), A1.1oy454 (described in U.S. Pat. No. 4,209,348), A11oy2
03E (described in U.S. Pat. No. 4,222,794), A
NASAIRloo from ir Research Corporation, ion.
またＣａｎｏｎ Ｍｕｓｋｅｇｏｎ Ｃｏｒｐｏｒａｔ
ｉｏｎより、ＣＭＳＸ−２（特開昭５７−８９４５１号
に記載）、Ｃ万５Ｘ−３（特開昭５９−１．９０３４２
号に記載）等のＬｌｉ結晶専用Ｎ４基超耐熱合金が開発
された。Also, Canon Muskegon Corporation
ion, CMSX-2 (described in JP-A-57-89451), Cman5X-3 (JP-A-59-1.90342)
N4-based super heat-resistant alloys exclusively for Lli crystals have been developed.
さらに、英国特許１，５５７，９００号、２，１５９，
１７４Ａ号、ヨーロッパ特許００６３５１］Ａ１号、米
国特許４，４０２，７７２号等においても単結晶Ｎｉ基
超超耐熱合金提案されている。Furthermore, British Patent No. 1,557,900, 2,159,
No. 174A, European Patent No. 006351] A1, US Pat. No. 4,402,772, etc. have also proposed single-crystal Ni-based super super heat-resistant alloys.
上記の単結高合金は、従来の多結晶合金に比べるとはる
かに優れたクリープ破断強度を有するが、ガスタービン
エンジンの効率向上のためには、さらにクリープ破断強
度が高く、耐酸化性の優れた合金が望まれている。また
、Ｒｅ等のあまりに高価な元素を使用することは望まし
くない。The single-crystal high alloys mentioned above have much better creep rupture strength than conventional polycrystalline alloys, but in order to improve the efficiency of gas turbine engines, they are required to have even higher creep rupture strength and excellent oxidation resistance. There is a need for alloys that Further, it is not desirable to use an extremely expensive element such as Re.
従来の単結晶合金は主としてＷ、Ｔａの増加により、ク
リープ破断強度の増加を図ってきたが、その添加量が過
度の場合、有害用析出等の間層があり、さらにクリープ
破断強度の高い合金の開発は容易ではない。例えば初期
に開発されたＡ１１ｏｙ４４４、Ａ１１ｏｙ４５４等の
合金のクリープ破断強度はまだ十分高くない。またＡ１
１ｏＹ２０３Ｅおよび英国特許１．５５７，９００号記
載の合金は高価なＲｅを使用するという問題点がある。Conventional single-crystal alloys have attempted to increase creep rupture strength mainly by increasing W and Ta, but if the amounts added are excessive, harmful interlayers such as precipitation may occur, and alloys with high creep rupture strength development is not easy. For example, the creep rupture strength of early developed alloys such as A11oy444 and A11oy454 is still not high enough. Also A1
The alloys described in 1oY203E and British Patent No. 1.557,900 have the problem of using expensive Re.
ＮＡＳＡＩＲｌｏｏはクリープ破断強度の増加を狙って
開発されたが、Ｗ量が高いため、α−Ｗ相やμ相などの
有害相が析出し、クリープ破断強度を低下させることが
見出されている。同様に英国特許２，１５９，１７４号
に記載の合金も、Ｗ。NASA Rloo was developed with the aim of increasing creep rupture strength, but it has been found that due to the high W content, harmful phases such as α-W phase and μ phase precipitate, reducing creep rupture strength. Similarly, the alloy described in British Patent No. 2,159,174 is W.
Ｔａ１ｌが高いため、α−Ｗ相等が析出すると考えられ
る。α−Ｗ相等の有害相の析出を防ぐためにはＷ、Ｍｏ
、Ｔａ等の添加量を少なくすることが必要であるが、必
要以上に少なくするとクリープ破断強度を低下させる。Since Ta1l is high, it is thought that α-W phase etc. are precipitated. In order to prevent the precipitation of harmful phases such as α-W phase, W, Mo
It is necessary to reduce the amount of addition of Ta, Ta, etc., but if it is reduced more than necessary, the creep rupture strength will be reduced.
ＣＭＳＸ−２，ＣＭＳＸ−３ハ、ａ −Ｗ 相ヤＩｔ
相ナト（１） 析出ヲ防ぎ、組織的に安定であることを
狙って開発された合金であるが、クリープ破断強度は十
分に高くない。また、ヨーロッパ特許００６３５１１Ａ
１号、ならびに米国特許４，４０２，７７２号に記載の
合金もクリープ破断強度は十分に高くない。CMSX-2, CMSX-3, a - W Aiya It
Phase Nut (1) This alloy was developed with the aim of preventing precipitation and being structurally stable, but its creep rupture strength is not sufficiently high. Also, European patent 0063511A
No. 1, as well as the alloys described in US Pat. No. 4,402,772, do not have sufficiently high creep rupture strength.
さらに、タービンブレードは高温にさらされるため耐酸
化性も重要な要求特性の−っである。Furthermore, since turbine blades are exposed to high temperatures, oxidation resistance is also an important required property.
般に耐酸化性はＣｒ、Ａ１等の元素の爪を増すことによ
り良くなるが、組織を安定化し、良好なりリープ破断強
度を得るためにはＣｒ、ＡＩ量も狭い範囲に限定される
ので良好な耐酸化性を得ることは容易ではない。In general, oxidation resistance is improved by increasing the number of elements such as Cr and Al, but in order to stabilize the structure and obtain good leap rupture strength, the amount of Cr and Al is also limited to a narrow range, so it is good. It is not easy to obtain good oxidation resistance.
本発明者らは、Ｒｅ等の高価な合金元素を使用せず、組
織的に安定でかつクリープ破断強度が優れる合金を開発
するため、合金元素の個々の添加量ならびに合金元素相
互の成分バランスについて、詳細な検討を行なった結果
、特開昭６２−１１６７４８号に開示したように重量％
でＣｒ４〜１０％、Ａ１４〜６．５％、Ｗ ４〜１０％
、Ｔａ４〜９％、Ｍｏ １．５〜６％、残部Ｎ１および
不純物からなり、かつｌ／２Ｗ＋１７２Ｔａ＋Ｍｏ−９
，５〜１３．５％であることを特徴とする単結晶Ｎｉ基
還耐熱合金を見出した。In order to develop an alloy that is structurally stable and has excellent creep rupture strength without using expensive alloying elements such as Re, the inventors investigated the amount of each alloying element added and the mutual composition balance of the alloying elements. As a result of detailed study, as disclosed in JP-A-62-116748, weight%
Cr4~10%, A14~6.5%, W 4~10%
, Ta 4-9%, Mo 1.5-6%, balance N1 and impurities, and 1/2W+172Ta+Mo-9
, 5 to 13.5%.A single crystal Ni-based reduced heat-resistant alloy has been found.
本発明者らは、前記合金のクリープ破断延性をさらに改
善した合金として、前記合金に１２％以下のＣＯを添加
した合金を見出した（特開昭６２−２９０８３９号に記
載）。The present inventors have discovered an alloy in which 12% or less of CO is added to the above alloy as an alloy that further improves the creep rupture ductility of the above alloy (described in JP-A-62-290839).
これらの合金は、クリープ破断強度および組織安定性に
優れるが、耐酸化性をさらに改善すれば、ガスタービン
エンジンのタービンブレードの寿命が一段と向上するで
あろうということがわかってきた。Although these alloys have excellent creep rupture strength and structural stability, it has been found that further improvements in oxidation resistance would further extend the life of turbine blades in gas turbine engines.
本発明の目的は、組織的に安定しかつクリープ破断強度
および耐酸化性のすぐれた単結晶Ｎｉ基超耐熱合金を提
供することである。An object of the present invention is to provide a single-crystal Ni-based superalloy that is structurally stable and has excellent creep rupture strength and oxidation resistance.
ここで本発明者らは、先に発明した合金をベースに、そ
の耐酸化性を向上させるための検討を行なった結果、本
発明を完成したものである。すなわち、本発明において
は、注意深く制御された量のＨｆならびにＣｏを添加す
ることにより、先に達成されたクリープ破断強度ならび
に組織安定性を損なわないまま、耐酸化性を大幅に向上
させることに成功した。The present inventors completed the present invention as a result of conducting studies to improve the oxidation resistance of the previously invented alloy. That is, in the present invention, by adding carefully controlled amounts of Hf and Co, we succeeded in significantly improving oxidation resistance without impairing the previously achieved creep rupture strength and structural stability. did.
本発明のうち第１の発明は、重量％でＣｒ４〜９％、Ａ
Ｉ ４〜６．５％、Ｗ ５〜８．５％、Ｔａ ５〜８．
５％、Ｍｏ ３〜６％、Ｈｆ ０．０１−０，３０％、
Ｃｏ ０．０１−４％、残部Ｎｉおよび不純物からなり
、かつＷ ＋Ｔａが１６％末滴であることを特徴とする
単結晶Ｎｉ基超耐熱合金であり、第２の発明は、重量％
にてＣｒ ４．５〜８．５％、Ａ１４〜６％、Ｗ ５．
５〜８．２％、Ｔａ ５．５〜８．２％、Ｍｏ ３．５
〜５．５％、Ｈｆ０．０５〜０．２５％、Ｃｏ ０．５
〜３％、残部Ｎｉおよび不純物からなり、かつＷ ＋Ｔ
ａが１６％未満であることを特徴とする単結晶Ｎｉ基
超耐熱合金である。The first invention of the present invention has Cr4 to 9% by weight, A
I 4-6.5%, W 5-8.5%, Ta 5-8.
5%, Mo 3-6%, Hf 0.01-0.30%,
The second invention is a single-crystal Ni-based super heat-resistant alloy consisting of 0.01-4% Co, the balance Ni and impurities, and 16% W + Ta as powder droplets.
Cr 4.5-8.5%, A14-6%, W 5.
5-8.2%, Ta 5.5-8.2%, Mo 3.5
~5.5%, Hf0.05~0.25%, Co0.5
~3%, the balance consists of Ni and impurities, and W +T
This is a single-crystal Ni-based super heat-resistant alloy characterized in that a is less than 16%.
以下に本発明合金の成分限定理由について述べる。The reasons for limiting the composition of the alloy of the present invention will be described below.
Ｃｒは合金の耐酸化性、耐食性を向上させる作用を持つ
が、過度の添加はσ相などの有害析出相を生じクリープ
破断強度を低下させるため、４〜９％に限定する。望ま
しくは４．５〜８．５％である。Cr has the effect of improving the oxidation resistance and corrosion resistance of the alloy, but excessive addition produces harmful precipitated phases such as σ phase and reduces creep rupture strength, so it is limited to 4 to 9%. It is preferably 4.5 to 8.5%.
ＡｉはＮｉ基超超耐熱合金析出強化するγ′相と呼ばれ
る金属間化合物を形成する主要元素である。Ai is a main element that forms an intermetallic compound called the γ' phase that strengthens the Ni-based super super alloy by precipitation.
γ′相は基本組成はＮｉ、ＡＩで表わされるが、ＡＩ以
外でもＴｉ、Ｔａ、Ｗ、Ｍｏなどを固溶することにより
更に強化される。これらの元素の作用は後で詳しく述べ
る。単結晶合金は通常体積率で５０％以上もの多量のγ
′相を含むが、凝固終了時には共晶γ′相と呼ばれる粗
大γ′相が存在するので、これを母相（γ相と呼ばれる
）中へ一旦固溶させるため高温で固溶化処理を行なう。The basic composition of the γ' phase is represented by Ni and AI, but it can be further strengthened by adding solid solutions other than AI such as Ti, Ta, W, and Mo. The effects of these elements will be described in detail later. Single-crystal alloys usually have a large amount of γ, with a volume fraction of more than 50%.
However, at the end of solidification, a coarse γ' phase called the eutectic γ' phase is present, so solution treatment is performed at a high temperature to temporarily dissolve this into the parent phase (referred to as the γ phase).
固溶化処理で固溶したγ′相は、冷却中およびその後の
時効処理により均一微細に析出することにより合金を強
化する。ＡＩは４％未満ではγ′相の生成基が十分でな
く、また６、５％を越えるとγ′相が多過ぎ、共晶γ′
相を固溶化処理で完全に固溶させることができないため
クリープ破断強度は低下する。従ってＡＩは４〜６．５
％に限定する。望ましくは４〜６％である。The γ' phase dissolved in the solid solution treatment strengthens the alloy by precipitating uniformly and finely during cooling and the subsequent aging treatment. If AI is less than 4%, there will not be enough γ' phase forming groups, and if it exceeds 6.5%, there will be too much γ' phase, resulting in eutectic γ'
Since the phases cannot be completely dissolved in the solid solution treatment, the creep rupture strength decreases. Therefore AI is 4-6.5
%. It is preferably 4 to 6%.
Ｗはγ相およびγ′相に固溶して両相を強化する元素で
あり、最低５％は必要である。しかしながら、過度の泳
方Ｕはα−Ｗ相と呼ばれる相を析出し、却ってクリープ
破断強度を低下させる。従ってＷは５〜８．５％に限定
する。望ましくは５．５〜８，２％である。W is an element that forms a solid solution in the γ phase and the γ' phase to strengthen both phases, and must be present in an amount of at least 5%. However, excessive swimming direction U causes a phase called α-W phase to precipitate, which actually reduces the creep rupture strength. Therefore, W is limited to 5 to 8.5%. It is preferably 5.5 to 8.2%.
Ｔａは主としてγ′相に固溶してγ′相を強化する。従
って最低５％は必要であるが、過度に添加すると共晶γ
′相を固溶させることが困難となり、またγ、γ′相の
格子定数のミスマツチを太き（することによりγ′相が
粗大化してクリープ破断強度が低Ｆするため、５〜８．
５％に限定する。９）ましくけ５．５〜８．２％である
。Ta mainly forms a solid solution in the γ' phase and strengthens the γ' phase. Therefore, it is necessary to add at least 5%, but if it is added too much, the eutectic γ
5 to 8. It becomes difficult to make the γ' phase a solid solution, and the mismatch in the lattice constants of the γ and γ' phases becomes thicker (by doing so, the γ' phase becomes coarser and the creep rupture strength becomes low F).
Limited to 5%. 9) It is 5.5 to 8.2%.
なお、Ｗ、Ｔａはその合計が１６％以上であると。Note that the total of W and Ta is 16% or more.
α−Ｗ相が析出しやすく、クリープ破断強度を低下させ
、また耐酸化性も悪くなるので、Ｗ 十Ｔ ａを１６％
未満に限定する。The α-W phase is likely to precipitate, lowering the creep rupture strength and also worsening the oxidation resistance, so W
limited to less than
Ｍａは一部γ′にも固溶するが、主としてγ相に固溶し
てγ相を強化するので最低３％は必要であるが、過度の
添加はα−Ｍｏ相を生じてクリープＩｌｌ断強度を低下
させるため、３〜６％に限定する。望ましくは３，５〜
５．５％である。Although a part of Ma also forms a solid solution in γ', it mainly dissolves in the γ phase and strengthens the γ phase, so a minimum amount of 3% is necessary; however, excessive addition may cause an α-Mo phase and lead to creep breakdown. In order to reduce the strength, it is limited to 3 to 6%. Preferably 3.5~
It is 5.5%.
以上述べたＷ、Ｔａ、Ｍｏの３元素はそれぞれ異なった
強化作用をもつため、３元素を共に添加することが重要
である。前述のＮＡＳＡＩＲ１００合金は、Ｗが１０．
５％と高いためα−Ｗ相の析出が見られ、これを改良し
たＣＭＳＸ−２合金およびＣＭＳＸ−３合金はＷを低め
、代わりにＴａを増加することによりα−Ｗ相の析出を
抑えているが、ＭＯが低いため固溶強化はまだ十分でな
い。同様に、ヨーロッパ特許００６３５１１Ａ１号、米
国特許４，４０２，７７２号に記載の合金もＭｏ添加量
が本発明合金より低く、固溶強化は十分でない。また、
英国特許２，１５９，１７４Ａ号に記載の合金は、Ｗ
十Ｔａが１６％以上であるため、α−Ｗ析出の危険性が
ある。Since the three elements W, Ta, and Mo mentioned above have different strengthening effects, it is important to add all three elements together. The aforementioned NASA AIR 100 alloy has W of 10.
5%, precipitation of the α-W phase is observed, and the improved CMSX-2 and CMSX-3 alloys suppress the precipitation of the α-W phase by lowering W and increasing Ta instead. However, solid solution strengthening is not yet sufficient due to the low MO content. Similarly, the alloys described in European Patent No. 0063511A1 and US Pat. No. 4,402,772 also have a lower amount of Mo added than the alloy of the present invention, and do not have sufficient solid solution strengthening. Also,
The alloy described in British Patent No. 2,159,174A is W
Since ten Ta is 16% or more, there is a risk of α-W precipitation.
本発明合金はＷ、Ｔａ、Ｍｏの３元素のうち特にＭ。The alloy of the present invention particularly contains M among the three elements W, Ta, and Mo.
の添加量を従来より高くし、各元素の添加量について詳
細に検討した結果、α−（Ｗ、Ｍｏ）等の有害相を生じ
ない範囲でγ、γ′相の固溶強化を最大としたものであ
る。As a result of a detailed study of the amount of each element added, we maximized the solid solution strengthening of the γ and γ′ phases without producing harmful phases such as α-(W, Mo). It is something.
Ｈｆは、例えば米国特許第４，１１６，７２３号に開示
される単結晶合金においては、特に添加が必要でないと
されている。これに対して本発明において、Ｈｆは耐酸
化性を改善するための重要な元素であり、積極的に添加
されるべきである。適正な量のＨｆの添加によりクリー
プ融断特性を低下させることなく耐酸化性を大幅に改善
できることが見出された。Ｉ−ｔ ｆはその効果を得る
ため最低０．０１％必要であるが、過度の添加は合金の
融点を下げるため固溶化処理温度を十分高くすることが
できず、共晶γ′相を固溶させることが困難であると共
に、組織を不安定にしクリープ破断強度を低下させるた
め０．０１〜０．３０％に限定する。望ましくは、０．
０５〜０．２５％である。It is said that addition of Hf is not particularly necessary in the single crystal alloy disclosed in, for example, US Pat. No. 4,116,723. On the other hand, in the present invention, Hf is an important element for improving oxidation resistance and should be actively added. It has been found that by adding an appropriate amount of Hf, oxidation resistance can be significantly improved without deteriorating creep-fusion properties. I-t f is required at least 0.01% to obtain this effect, but excessive addition lowers the melting point of the alloy, making it impossible to raise the solution treatment temperature sufficiently, and solidifying the eutectic γ' phase. Since it is difficult to dissolve and also makes the structure unstable and lowers the creep rupture strength, it is limited to 0.01 to 0.30%. Preferably, 0.
05-0.25%.
ＣＯは、米国特許第４．１．１６，７２３号（Ａｌ １
ｏｙ４４４）に上れば、ＴＣＰ相と呼ばれる有害相を形
成し易いため、不純物レベル以下に抑えられている。し
かしながら、Ｇ Ｏはその添加量を適正にし、かつＣｏ
以外の元素の添加量を注意深く限定すれば、、ＴＣＩ）
相の生成が防止できるだけでなく、Ｈｆと共に適正量添
加することにより、耐酸化性をさらに向上させる作用を
持つことが新たに見出された。よって、本発明合金では
ＣＯはＨｆとの共同添加が必要で、ＣＯを０．０１％以
上添加する。しかし、４％を越えて添加すると耐酸化性
はかえって悪くなるので、４％以下に限定する。望まし
くは、０．５〜３％である。CO is described in U.S. Pat. No. 4.1.16,723 (Al 1
oy444), it tends to form a harmful phase called TCP phase, so it is kept below the impurity level. However, GO should be added in an appropriate amount and Co
If the amount of added elements other than .TCI) is carefully limited,
It has been newly discovered that it not only prevents the formation of phases, but also has the effect of further improving oxidation resistance by adding an appropriate amount together with Hf. Therefore, in the alloy of the present invention, CO needs to be added together with Hf, and 0.01% or more of CO is added. However, if it is added in an amount exceeding 4%, the oxidation resistance will deteriorate, so it is limited to 4% or less. Desirably, it is 0.5 to 3%.
なお、前述のＣＭＳＸ−３合金はＣＭＳＸ−２合金に少
量のＨｆを添加した合金であるが、ＣＯが４％以上であ
るため耐酸化性はまだ十分ではない。同様に米国特許４
，４０２，７７２号に記載の合金にもＨｆが添加されて
いるが、ＣＯが４％以上であるため、耐酸化性は十分で
ないと思われる。Note that the above-mentioned CMSX-3 alloy is an alloy in which a small amount of Hf is added to the CMSX-2 alloy, but since the CO content is 4% or more, the oxidation resistance is still not sufficient. Similarly, US Patent 4
Although Hf is also added to the alloy described in No. 402,772, since the CO content is 4% or more, the oxidation resistance is considered to be insufficient.
なお、従来の単結晶合金にはＴｉが添加されていること
が多い。Ｔｉはγ′相に固溶し、γ′相の形成ならびに
固溶強化に役立つが、共晶γ′相をつくりやすく、かつ
合金の融点を下げるため、固溶化処理温度を十分高くす
ることができず、共晶γ′相を固溶させることが困難で
ある。従って、本発明合金にはＴｉを無添加とした。Note that Ti is often added to conventional single crystal alloys. Ti forms a solid solution in the γ' phase and is useful for the formation of the γ' phase and solid solution strengthening.However, in order to facilitate the formation of the eutectic γ' phase and to lower the melting point of the alloy, the solution treatment temperature must be set sufficiently high. It is difficult to form a solid solution of the eutectic γ' phase. Therefore, no Ti was added to the alloy of the present invention.
他の単結晶合金と同様、本発明合金においても、Ｃ，Ｂ
、Ｚｒ等は合金の初期溶融温度を低めるため、不純物レ
ベルに抑えることが必要である。Similar to other single crystal alloys, the alloy of the present invention also contains C, B
, Zr, etc., lower the initial melting temperature of the alloy, and therefore need to be suppressed to an impurity level.
第１表に本発明合金、比較合金および従来合金の特性を
比較するために用いた試料の化学成分、各合金のクリー
プ破断時間（試験条件は表中に示す）および１１００℃
で１６時間加熱を１０回繰り返した後の酸化減量を測定
した結果を示す。Table 1 shows the chemical composition of the samples used to compare the properties of the inventive alloy, comparative alloy, and conventional alloy, the creep rupture time of each alloy (test conditions are shown in the table), and 1100°C
The results of measuring the oxidation loss after heating was repeated 10 times for 16 hours are shown.
単結晶試料にはそれぞれの合金に適正な次の熱処理を施
した。すなわち本発明合金および比較台金はすべて１３
１Ｏ〜１３４５℃で４時間加熱後空冷、さらに１０８０
℃で５時間加熱後空冷、さらに８７０ ’Ｃで２０時間
加熱後空冷の熱処理、従来合金ＮＡＳＡＩＲ１００は、
１３２０℃で４時間加熱後空冷、さらに９８０ ℃で５
時間加熱後空冷、さらに８７０℃で２０時間加熱後空冷
の熱処理、従来合金ＣＭＳＸ−２は１３１６℃で４時間
加熱後空冷、さらに９８０℃で５時間加熱後空冷、さら
に８７０℃で２０時間加熱後空冷、従来合金ＣＭＳＸ−
３は１３０２℃で４時間加熱後空冷、さらに９８０℃で
５時間加熱後空冷、さらに８７０℃で２０時間加熱後空
冷の熱処理を行なった６
比較合金のうちＮｏ、 １ｌ−Ｎｏ、１３合金はＣｏ、
Ｈｆ以外の成分は本発明合金と同一であり、クリープ破
断強度は高いが、Ｃ０１Ｈｆを添加していないため耐酸
化性は良くない。Ｎｏ、１４合金はＷ＋Ｔａが１６％以
上のためクリープ破断強度はあまり高くなく、耐酸化性
も悪い、 Ｎｏ、１５、Ｎｏ、１６合金はＣｏが４％以
上のため耐酸化性が悪い。Ｎｏ、１７〜Ｎｏ、２０合金
はＷ、Ｔａ、Ｍｏのうち１つ以上が本発明合金の成分範
囲をはずれており、クリープ破断強度は本発明合金より
大幅に低い。また従来合金（Ａｌｌｏｙ４４４のデータ
は、米国特許４．］１６，７２３号から引用したもの）
も本発明合金に比ベクリープ敏断強度、耐酸化性共大幅
に低い値を示す。The single crystal samples were subjected to the following heat treatments appropriate for each alloy. That is, the alloy of the present invention and the comparative base metal are all 13
After heating at 10 to 1345℃ for 4 hours, air cooling and further heating to 1080℃.
The conventional alloy NASA AIR 100 was heated at 870'C for 5 hours and then air cooled, and then heated at 870'C for 20 hours and then air cooled.
After heating at 1320℃ for 4 hours, air cooling, and then heating at 980℃ for 5 hours.
The conventional alloy CMSX-2 is heated at 1316°C for 4 hours, then air cooled, then heated at 980°C for 5 hours, air cooled, and further heated at 870°C for 20 hours. Air-cooled, conventional alloy CMSX-
3 was heated at 1302°C for 4 hours and then air cooled, further heated at 980°C for 5 hours and then air cooled, and further heated at 870°C for 20 hours and air cooled. 6 Among the comparative alloys, No, 1l-No, and 13 alloys were Co ,
The components other than Hf are the same as the alloy of the present invention, and the creep rupture strength is high, but the oxidation resistance is poor because no C01Hf is added. The No. 14 alloy has a W+Ta content of 16% or more, so its creep rupture strength is not very high, and its oxidation resistance is poor. The No. 15, No. 16 alloy has a Co content of 4% or more, so its oxidation resistance is poor. In alloys No. 17 to No. 20, one or more of W, Ta, and Mo is outside the composition range of the alloy of the present invention, and the creep rupture strength is significantly lower than that of the alloy of the present invention. Also, conventional alloys (data for Alloy 444 are taken from U.S. Pat. No. 4.] 16,723)
The alloys of the present invention also exhibit significantly lower creep strength and oxidation resistance than the alloys of the present invention.
これに対し本発明台金はクリープ破断強度、耐酸化性共
にすぐれていることが明らかである。In contrast, it is clear that the base metal of the present invention has excellent creep rupture strength and oxidation resistance.
〔発明の効果〕
以上のようシこ、本発明合金は既存合金に比べて優れた
クリープ破断強度および耐酸化性を有するため、ガスタ
ービンブレードに用いてその効率向上に大きく寄与する
ものである。[Effects of the Invention] As described above, since the alloy of the present invention has superior creep rupture strength and oxidation resistance compared to existing alloys, it can be used in gas turbine blades and greatly contributes to improving the efficiency thereof.
Claims (1)
〜８．５％、Ｔａ５〜８．５％、Ｍｏ３〜６％、Ｈｆ０
．０１〜０．３０％、Ｃｏ０．０１〜４％、残部Ｎｉお
よび不純物からなり、かつＷ＋Ｔａが１６％未満である
ことを特徴とする単結晶Ｎｉ基超耐熱合金。 ２ 重量％にてＣｒ４．５〜８．５％、Ａｌ４〜６％、
Ｗ５．５〜８．２％、Ｔａ５．５〜８．２％、Ｍｏ３．
５〜５．５％、Ｈｆ０．０５〜０．２５％、Ｃｏ０．５
〜３％、残部Ｎｉおよび不純物からなり、かつＷ＋Ｔａ
が１６％未満であることを特徴とする単結晶Ｎｉ基超耐
熱合金。[Claims] 1% by weight: Cr4-9%, Al4-6.5%, W5
~8.5%, Ta5~8.5%, Mo3~6%, Hf0
．． 1. A single-crystal Ni-based super heat-resistant alloy comprising 0.01 to 0.30% Co, 0.01 to 4% Co, the balance Ni and impurities, and W+Ta less than 16%. 2% by weight Cr4.5-8.5%, Al4-6%,
W5.5-8.2%, Ta5.5-8.2%, Mo3.
5-5.5%, Hf0.05-0.25%, Co0.5
~3%, the balance consists of Ni and impurities, and W+Ta
1. A single-crystal Ni-based super heat-resistant alloy, characterized in that the amount is less than 16%.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1030172A JP2552351B2 (en) | 1988-05-17 | 1989-02-09 | Single crystal Ni-based super heat resistant alloy |
| GB8911169A GB2220422B (en) | 1988-05-17 | 1989-05-16 | Heat resistant single-crystal nickel-base super alloy |
| US07/469,740 US4976791A (en) | 1988-05-17 | 1990-01-19 | Heat resistant single crystal nickel-base super alloy |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-120023 | 1988-05-17 | ||
| JP12002388 | 1988-05-17 | ||
| JP1030172A JP2552351B2 (en) | 1988-05-17 | 1989-02-09 | Single crystal Ni-based super heat resistant alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02138431A true JPH02138431A (en) | 1990-05-28 |
| JP2552351B2 JP2552351B2 (en) | 1996-11-13 |
Family
ID=26368470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1030172A Expired - Fee Related JP2552351B2 (en) | 1988-05-17 | 1989-02-09 | Single crystal Ni-based super heat resistant alloy |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4976791A (en) |
| JP (1) | JP2552351B2 (en) |
| GB (1) | GB2220422B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916382A (en) * | 1992-03-09 | 1999-06-29 | Hitachi, Ltd. | High corrosion resistant high strength superalloy and gas turbine utilizing the alloy |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5443789A (en) * | 1992-09-14 | 1995-08-22 | Cannon-Muskegon Corporation | Low yttrium, high temperature alloy |
| CA2440573C (en) * | 2002-12-16 | 2013-06-18 | Howmet Research Corporation | Nickel base superalloy |
| US8216509B2 (en) | 2009-02-05 | 2012-07-10 | Honeywell International Inc. | Nickel-base superalloys |
| US20100329921A1 (en) * | 2009-06-30 | 2010-12-30 | Joshua Leigh Miller | Nickel base superalloy compositions and superalloy articles |
| CN111433378B (en) * | 2017-11-29 | 2021-10-08 | 日立金属株式会社 | Ni-based alloy for hot die, hot forging die using same, and method for producing forged product |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5864331A (en) * | 1981-09-19 | 1983-04-16 | ロ−ルス・ロイス・ピ−エルシ− | Alloy suitable for manufacture of single crystal casted article and casted article therefrom |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3526499A (en) * | 1967-08-22 | 1970-09-01 | Trw Inc | Nickel base alloy having improved stress rupture properties |
| GB1260982A (en) * | 1970-06-08 | 1972-01-19 | Trw Inc | Improvements in or relating to nickel base alloys |
| US4209348A (en) * | 1976-11-17 | 1980-06-24 | United Technologies Corporation | Heat treated superalloy single crystal article and process |
| US4116723A (en) * | 1976-11-17 | 1978-09-26 | United Technologies Corporation | Heat treated superalloy single crystal article and process |
| FR2374427A1 (en) * | 1976-12-16 | 1978-07-13 | Gen Electric | PERFECTED NICKEL-BASED ALLOY AND CAST PART OBTAINED FROM THIS ALLOY |
| US4222794A (en) * | 1979-07-02 | 1980-09-16 | United Technologies Corporation | Single crystal nickel superalloy |
| EP0052911B1 (en) * | 1980-11-24 | 1985-09-18 | Cannon-Muskegon Corporation | Single crystal (single grain) alloy |
| FR2503188A1 (en) * | 1981-04-03 | 1982-10-08 | Onera (Off Nat Aerospatiale) | MONOCRYSTALLINE SUPERALLIAGE WITH MATRIX MATRIX BASED ON NICKEL, PROCESS FOR IMPROVING WORKPIECES IN THIS SUPERALLIATION AND PARTS OBTAINED THEREBY |
| US4402772A (en) * | 1981-09-14 | 1983-09-06 | United Technologies Corporation | Superalloy single crystal articles |
| JPS59190342A (en) * | 1983-04-08 | 1984-10-29 | キヤノン−マスキ−ガン・コ−ポレイシヨン | Single crystal alloy |
| GB2159174A (en) * | 1984-05-25 | 1985-11-27 | Rolls Royce | A nickel-base alloy suitable for making single-crystal castings |
| JPS62116748A (en) * | 1985-11-18 | 1987-05-28 | Hitachi Metals Ltd | Superheat resistant single crystalline ni alloy |
| JPH0765134B2 (en) * | 1986-06-11 | 1995-07-12 | 日立金属株式会社 | Single crystal Ni-based super heat resistant alloy |
-
1989
- 1989-02-09 JP JP1030172A patent/JP2552351B2/en not_active Expired - Fee Related
- 1989-05-16 GB GB8911169A patent/GB2220422B/en not_active Expired - Lifetime
-
1990
- 1990-01-19 US US07/469,740 patent/US4976791A/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5864331A (en) * | 1981-09-19 | 1983-04-16 | ロ−ルス・ロイス・ピ−エルシ− | Alloy suitable for manufacture of single crystal casted article and casted article therefrom |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916382A (en) * | 1992-03-09 | 1999-06-29 | Hitachi, Ltd. | High corrosion resistant high strength superalloy and gas turbine utilizing the alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8911169D0 (en) | 1989-07-05 |
| JP2552351B2 (en) | 1996-11-13 |
| GB2220422A (en) | 1990-01-10 |
| GB2220422B (en) | 1991-06-26 |
| US4976791A (en) | 1990-12-11 |
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